EP1330503B1 - Compositions contenant des polyhydroxyalcanoates et des monomères réactifs - Google Patents

Compositions contenant des polyhydroxyalcanoates et des monomères réactifs Download PDF

Info

Publication number
EP1330503B1
EP1330503B1 EP01988751A EP01988751A EP1330503B1 EP 1330503 B1 EP1330503 B1 EP 1330503B1 EP 01988751 A EP01988751 A EP 01988751A EP 01988751 A EP01988751 A EP 01988751A EP 1330503 B1 EP1330503 B1 EP 1330503B1
Authority
EP
European Patent Office
Prior art keywords
polyhydroxyalkanoate
hot melt
melt adhesive
composition
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01988751A
Other languages
German (de)
English (en)
Other versions
EP1330503A2 (fr
Inventor
Robert S. Whitehouse
Luhua Zhong
Sean Daughtry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yield10 Bioscience Inc
Original Assignee
Metabolix Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Metabolix Inc filed Critical Metabolix Inc
Publication of EP1330503A2 publication Critical patent/EP1330503A2/fr
Application granted granted Critical
Publication of EP1330503B1 publication Critical patent/EP1330503B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C19/00—Cheese; Cheese preparations; Making thereof
    • A23C19/14—Treating cheese after having reached its definite form, e.g. ripening, smoking
    • A23C19/16—Covering the cheese surface, e.g. with paraffin wax
    • A23C19/163—Covering the cheese surface, e.g. with paraffin wax with a non-edible liquid or semi-liquid coating, e.g. wax, polymer dispersions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P20/00—Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
    • A23P20/10—Coating with edible coatings, e.g. with oils or fats
    • A23P20/11—Coating with compositions containing a majority of oils, fats, mono/diglycerides, fatty acids, mineral oils, waxes or paraffins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/28—Non-macromolecular organic substances

Definitions

  • the present invention relates to hot melt adhesive compositions, wax compositions, and coating compositions, and methods of using the same.
  • Hot melt adhesives are used in a great number of applications and are particularly employed in packaging materials for all sorts of goods. Unfortunately, most conventional hot melt adhesives are non-biodegradable, thus adversely affecting the environment. Those products that claim to be biodegradable are typically based on water sensitive polymers or additives and hence the degradation process is through dissolution rather than biodegradation. A need exists for a biodegradable hydrophobic hot melt adhesive composition that will provide sufficient adhesion for its intended use yet degrade years later and, thus, be environmentally friendly.
  • Non-stable products particularly food products such as cheese
  • a synthetic, non-biologically degradable plastic rind to improve product maturation and shelf-life.
  • the plastic of such a rind cannot be recovered or recycled and thus presents a problem for the environment.
  • a coating must fulfill a large number of functions and a large number of requirements.
  • the coating material must serve to prevent mechanical damage and attack by molds.
  • the coating must offer both mechanical and hygienic protection, and it must be easy to apply, for example, by an immersion coating technique or by coating with a sponge or brush.
  • Cheese coatings should advantageously affect the luster and rind formation and must adhere well to the wet surface or the cheese. In addition, after drying, the coating must not crack or stick, for example, to cutting hoards or other cheeses.
  • the coating should also be semi-impermeable since CO2 and certain flavoring components must be able to diffuse through the coating in order not to adversely affect maturing of the cheese. Water vapor must also be allowed to pass through in a controlled manner so that natural maturing can occur without any question or excessive weight loss. Also, components must not diffuse into the cheese from the coating.
  • the coating must keep well during prolonged storage. Any paraffinic wax layer that is subsequently applied to the latex coating must not peel off after vacuum packaging. In addition, machines used to apply the coating must be easy to clean.
  • the present invention relates, in part, to polyhydroxyalkanoate-containing hot melt adhesive, protective coating, and surface active agent compositions.
  • the polyhydroxyalkanoate useful in the present invention is an oligomer having a low molecular weight as defined in the claims.
  • the polyhydroxyalkanoate oligomer has a number average molecular weight that is from about to about 8,000, and most preferably, from 500 to about 3,000.
  • the number average molecular weight of the oligomer is greater than about 1,000. for example, from greater than about 1,000 up to about 50,000, or from greater than about 1,000 up to about 8,000.
  • compositions generally include one or more low molecular weight polyhydroxyalkanoates, one or more polyhydroxyalkanoates derived to contain one or more specified terminal groups, or a solution of one or more of such polyhydroxyalkanoates.
  • Useful polyhydroxyalkanoates and methods of making the same are described in U.S. Patent Application Nos. 60/218,384 , 60/225,902 , and 60/227,127 .
  • the compositions may include additional (optional) components to enhance processing or properties of the compositions or end products in which they are employed.
  • PHAs polyhydroayalkanoates
  • a number of bacteria which produce copolymers of D-3-hydroxybutyric acid and one or more long side chain hydroxyacid units containing from five to sixteen carbon atoms have been identified more recently ( Steinbuchel & Wiese, Appl. Microbiol. Biotechnol., 37:691-97 (1992 ); Valentin et al., Appl. Microbiol.
  • Hot melt adhesives are also disclosed in U.S. Patent Nos. 4,985,535 ; 5,583,187 ; 5,753,765 ; 5,900,473 ; 5,939,488 ; 5,939,499 ; and 5,952,405 .
  • the low molecular weight PHAs exhibit a number average molecular weight of from 500 to under 50,000, for example, under 20,000, more preferably from 500 to about 8,000, and most preferably from 500 to about 3,000.
  • the number average molecular weight of the oligomer is greater than about 1,000, for example, from greater than about 1000 up to about 50,000, or from greater than about 1.000 up to about 8.000.
  • the molecular weight of the PHAs is less than about 20.000 and preferably from 500 to about 9,500 or lower.
  • Another suitable molecular weight range for purposes of the present invention is from 500 to about 5,000, or from 500 to about 1,000. For hot melt adhesive applications, lower molecular weight PHAs in these ranges are more desirable than the higher molecular weight PHAs in these ranges.
  • Suitable monomeric units include hydroxybutyrate, hydroxyvalerate, hydroxyhexanoate, hydroxyheptanoate, hydroxypropanoate, hydroxyoctanoate, hydroxynonanoate, hydroxydecanoate, hydroxyundecanoate, and hydroxydodecanoate units.
  • PHAs including monomers and polymers (homopolymers, copolymers, and the like) and derivatives of 3-hydroxyacids, 4-hydroxyacids, 3-hydroxyacids, polylactic acid, and polyglycolic acid, or combinations thereof can be used. Representative PHAs are described in Steinbüchel & Valentin, FEMS Microbiol. Lett., 128:219-28 (1995 ).
  • Preferred PHAs include, but are not limited to, polyhydroxybutyrate; a copolymer of hydroxybutyric acid and hydroxyvaleric acid (e.g., a copolymer of 1-99 weight % hydroxy butyric acid and 1-99 weight % hydroxyvaleric acid): a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid (e.g..
  • a copolymer of 1-99 weight % 3-hydroxybutyric acid and 1-99 weight % 4-hydroxybutyric acid polylydroxyhexanoate; polyhydroxyoctanoate: a copolymer containing hydroxyhexanoate or hydroxyoctanoate groups randomly distributed through the polymer chain (e.g., at least 10 % by molar mass hydroxyoctanoate groups randomly distributed through the polymer chain of a copolymer); and combinations thereof.
  • the polyhydroxyoctanoate can also have end chain functionalities such as groups selected from vinyl; carboxylic acid: carboxylic acid ester; acetate; butyrate; propanoate; primary, secondary, or tertiary alcohol; amide; and/or a polyhydric alcohol.
  • the PHA can have the formula H[OCHR 7 (CH 2 ) n CO] p OR'.
  • the PHA can have the formula R"CO[OCHR k (CH 2 ) n CO] p OH.
  • the PHA can also be a block polymer containing polyhydroxyalkanoate segments and at least one polyalkylene glycol segment.
  • the block polymer preferably contains at least 20 weight % of a PHA segment and at least one polyalkylene glycol segment selected from one or more repeat units or ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof.
  • p is from 5 to 1000
  • n is 0 or an integer
  • R' is derived from a monohydric alcohol or a polyhydric alcohol, such as methyl-styryl
  • R" is derived from a carboxylic acid having I to 20 carbon atoms, such as methyl-styryl
  • R 5 , R 6 , R 7 , and R 8 can represent saturated or unsaturated hydrocarbon radicals: halo, hydroxy, oxygen or nitrogen substituted radicals: or hydrogen atoms, such as H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , or C 5 H 11 .
  • biodegradable polyhydroxyalkanoates can have at least one of the terminal end groups selected from:
  • Preferred PHAs useful in the compositions and methods of the present invention include the following formulae wherein the various variables arc as described above.
  • H(OCHRCH 2 CO) n OH H(OCHRCH 2 CO) n OR' where R' is preferably an alkyl group or substituted alkyl group (e.g. diol. polyol, etc) H(OCHRCH 2 CO) n O - M + where M + is preferably selected from ammonium, sodium, potassium, zinc.
  • R"CO(OCHRCH 2 CO) n OH where R" is preferably the alkyl group from an aliphatic carboxylic acid R"CO(OCHRCH 2 CO) n OR' where R" is preferably the alkyl group from an aliphatic carboxylic acid and R' is preferably an alkyl group or substituted alkyl group ( e.g. diol. polyol, etc.) R"CO(OCHRCH 2 CO) n O - M + where R" is preferably the alkyl group from an aliphatic carboxylic acid and M + is preferably selected from ammonium, sodium, potassium, zinc. and calcium.
  • C-X-D (IV) where C is a polyalkylene oxide unit comprising ethylene oxide structural units, propylene oxide structural units, or mixtures of ethylene oxide and propylene oxide structural units in a block or a random array with the proviso that if the array is a block array containing ethylene oxide structural units the array contains terminal ethylene oxide blocks, and wherein the total number of ethylene oxide and propylene oxide structural units in C is from about 1 to about 100, preferably from about 5 to about 40, and more preferably wherein greater than about 60% of the total repeat units arc ethylene oxide units, X is the X component shown in formula (II) above, and D is an alkyl ester having from about 1 to about 20 carbon atoms or OM where M is hydrogen, sodium, potassium, or ammonium: E-X-F (V) where E is X component shown in formula (11) above: C-X-D (IV) where C is a polyalkylene oxide unit comprising ethylene oxide structural units, propylene oxide structural units,
  • X is the X component shown in formula (II) above, and F is selected from a polyalkylene oxide structural unit containing ethylene oxide structural units, propylene oxide structural units, or a mixture of ethylene oxide and propylene oxide structural units in a block array or a random array with the proviso that if the array is a block array containing ethylene oxide structural units the array contains terminal ethylene oxide blocks, and wherein the total number of ethylene oxide and propylene oxide structural units in F is from about 1 to about 100, more preferably from about 5 to about 40.
  • ethylene oxide units -OCH 2 CH 2 N(R') 2 where R' is hydrogen or an ethylene oxide unit containing from about 1 to about 20 repeat units.
  • R' is hydrogen or an ethylene oxide unit containing from about 1 to about 20 repeat units.
  • -N(CH 2 CH 2 OR")R"' where each of R" and R"' is independently a hydrogen atom or an ethylene oxide structural unit containing from about 1 unit to about 20 repeating units.
  • R" is either a hydrogen atom or an ethylene oxide structural unit containing from about 1 unit to about 20 repeating units, or a polyol that may be subsequently ethoxylated, wherein the polyol is selected from glycerol, trimethylol propane, or sucrose; or G-X-H (VI) where X is the X component shown in formula (II) above, G is selected from a polyalkylene oxide structural unit containing ethylene oxide structural units, propylene oxide structural units, or a mixture of ethylene oxide and propylene oxide structural units in a block array or a random array with the proviso that if the array is a block array containing ethylene oxide structural units the array contains terminal ethylene oxide blocks, and wherein the total number of ethylene oxide and propylene oxide structural units in H is from about I to about 100, more preferably from about 5 to about 40.
  • H is selected from a polyalkylene oxide structural unit containing ethylene oxide structural units, propylene oxide structural units, or a mixture of ethylene oxide and propylene oxide structural units in a block array or a random array with the proviso that if the array is a block array containing ethylene oxide structural units the array contains terminal ethylene oxide blocks, and wherein the total number of ethylene oxide and propylene oxide structural units in F is from about I to about 100, more preferably from about 5 to about 40, and more preferably wherein greater than about 60% of the total repeat units are ethylene oxide units.
  • R' is hydrogen or an ethylene oxide unit containing from about 1 to about 20 repeat units.
  • -N(CH 2 CH 2 OR")R"' where each of R" and R''' is independently a hydrogen atom or an ethylene oxide structural unit containing from about 1 unit to about 20 repeating units.
  • -OCH 2 CH 2 N(CH 2 CH 2 OR") where R"" is either a hydrogen atom or an ethylene oxide structural unit containing from about 1 unit to about 20 repeating units, or a polyol that may be subsequently ethoxylated, wherein the polyol is selected from glycerol, trimethylol propane, or sucrose.
  • the present invention also relates to a group of alkanoic acid ester oligomers having a number average molecular weight of greater than about 1000 and having one or more of the following formulae: R' ⁇ OCHR(CH 2 ) n CO ⁇ m OCH 2 CH 2 OR' (VII) wherein R represents a hydrogen atom or an alkyl group having from about 1 to about 18 carbon atoms. R' represents a hydrogen atom or an acetate group, n is from about I to about 3.
  • R' is a hydrogen atom or an acetate group, n is from about 1 to about 3, and m is from about 1 to about 3; or
  • R" represents a hydrogen atom or an alkyl group having from about 1 to about 10 carbon atoms, n is from about 1 to about 3, m is from about 1 to about 3, and said oligomer has the following Hansen solubility parameters:
  • the present invention also relates to a group of alkanoic acid ester oligomers having a number average molecular weight of greater than about 1,000 and having one or more of the following formulae: R'(OCHR - CH 2 ) p ⁇ OCHR(CH 2 ) n CO ⁇ m OR" (X) wherein R represents a hydrogen atom or an alkyl group having from about 1 to about 18 carbon atoms. R' represents a hydrogen atom or an acetate group. R" is a hydrogen atom or and alkyl group having from about 1 to about 18 carbon atoms: n is from about 1 to about 3. m is from about 1 to about 30.
  • R" represents a hydrogen atom or a methyl group, n is from about 1 to about 3, and m is from about 1 to about 30, and q is from about 1 to about 100: or R'(OCHR'CH 2 ) p ⁇ OCHR(CH 2 ) n CO ⁇ m (OCH 2 CHR") 4 OR" (XII) wherein R represents a hydrogen atom or an alkyl group having from about 1 to about 18 carbon atoms.
  • R' represents a hydrogen atom or a methyl group
  • R" represents a hydrogen atom or an alkyl group having from about 1 to about 18 carbon atoms
  • n is from about 1 to about 3.
  • m is from about 1 to about 30.
  • p is from about 1 to about 100
  • q is from about 1 to about 100.
  • alkanoic acid ester oligomers of formulae (X)- (XII) are well suited as surface active agents and are preferably biodegradable.
  • the present invention also provides solutions or liquid mixtures that include an alkanoic acid ester oligomer surface active agent of formula (X), (XI) or (XII).
  • the hydrolysis of polyhydroxyalkanoates can occur in the presence of a strong acid catalyst such as sulfuric acid, hydrochloric acid or phosphoric acid; the most preferable being sulfuric or hydrochloric acids.
  • the resultant oligomers contain a terminal hydroxyl and carboxylic acid groups. If the reaction is carried out in the presence of a strong acid catalyst and an alcohol, then the oligomers will have terminal hydroxyl and ester groups. If the reaction is carried out in the presence of a strong acid catalyst and a carboxylic acid, then the oligomers will have an ester group generated from the carboxylic acid and the hydroxyl group on the oligomers, and a free carboxylic acid.
  • the low molecular weight PHA can also be prepared by the thermolysis of a higher molecular weight PHA such as one having a molecular weight of greater than about 80.000.
  • the thermolysis conditions can be as follows. Alkenoic acid oligomers can be obtained in high yield by the thermal treatment of polyhydroxyalkanoates at sufficient temperatures, such as from about 160°C to about 250°C at atmospheric pressure for a sufficient period, such as from about 1 minute to about 4 hours.
  • the alkyl group would be expected to have an impact on the glass transition temperature of the resultant polymer: as the number of carbon atoms in the alkyl chain increases, then the glass transition temperature (Tg) of the polymer will decrease.
  • these higher alkenoic acids derivatives can produce dual functionality, i.e., adhesion or crosslinking through the acid /ester group and hydrophobicity/Tg reduction through the alkyl group.
  • the PHA compositions can be prepared using PHAs in their solid form, in a latex form, in aqueous dispersions, or in solution, for example, dissolved in a solvent such as acetone. PHAs can be plasticized and blended with other polymers or agents.
  • PHAs having a wide range of polymer physical properties, can be produced, depending on the hydroxyacid monomer composition used ( Steinbuchel & Valentin, FEMS Microbiol. Lett.. 128:219-28 (1995 )).
  • the range of properties include, for example, melting temperatures between about 40°C and 180°C, glass transition temperatures between about -55°C to 5°C. degrees of crystallinity between about 0 % and 80 %, and elongation to break between about 5 and 500 %.
  • the rate of crystallization can be controlled.
  • Polyhydroxybutyrate for example, has characteristics similar to those of polypropylene, while polyhydroxyoctanoates (a copolymer of D-3-hydroxyoctanoate and D-3-hydroxyhexanoate) and poly-D-4-hydroxybutyrate behave more as elastomers, and PHAs with longer side chains have characteristics similar to waxes.
  • the range of PHA polymers available with melting temperatures ranging from about 40°C to about 180°C provides additional flexibility in shape formation. As the molecular weight is reduced, the Tg remains relatively constant however the Tm is reduced. At low molecular weights ( ⁇ 50,000), the end chain units start to have an impact on physical properties.
  • One particularly useful form is as a latex or PHA in water. Evaporation of the water as the shapes are molded result in film formation as the PHA granules coalesce providing excellent binding. The PHAs are readily removed by degradation during the subsequent thermal processing of the shaped parts.
  • the range of PHA polymers available with melting temperatures ranging from about 40°C to about 180°C provides additional flexibility in shape formation.
  • the monomer compositions can also affect solubility in organic solvents, allowing the choice of a wide range of solvents.
  • Copolymers of D-3-hydroxybutyrate and other hydroxyacid co-monomers have significantly different solubility characteristics from those of the PHB homopolymer.
  • acetone is not a good solvent for PHB but is very useful for dissolving D-3-hydroxybutyrate copolymers with D-3-hydroxyacids containing from 6 to 13 carbon atoms ( Abe et al.. Int. J. Biol. Macromol. 16:115-19 (1994 ): Kato et al., Appl. Microbiol. Biotechnol., 45:363-70 (1996 )).
  • the alkenoic acids can be destroyed by thermal catalytic systems, by combustion, or a combination thereof.
  • the need for air inflow, oxygen, or other oxidants is eliminated or reduced through the use of PHA binders, thereby reducing waste gas emissions and heat loss. Avoidance of oxidants also minimizes undesirable oxidation of components such as metal powders.
  • PHAs are also compatible with a reducing or inert atmosphere, when exposure to such atmospheres is desired. For example, the use of reducing atmospheres is advantageous when using metal oxides or mixtures comprising metal oxides.
  • the hot melt adhesive compositions of the present invention have a glass transition temperature and a melt viscosity that together provides a softening point of from about 25°C to about 200°C, more preferably, from about 50°C to about 150°C, for example, from about 85°C to about 115°C.
  • the polyhydroxyalkanoates can be modified to include a terminal reactive group such as one or more of the reactive groups mentioned above.
  • the reactive monomer can be included in the hot melt adhesive compositions of the present invention in an amount of from about 5 wt% to about 95 wt%, more preferably from about 35 wt% to about 55 wt%, based on the total weight of the adhesive composition.
  • paraffin waxes useful herein are those having a ring and ball softening point of about 55°C to about 85°C.
  • Preferred paraffin waxes are Okerin® 236 TP available from Astor Wax Corporation located in Doraville. Ga.: Penreco® 4913 available from Pennzoil Products Co. in Houston. Tex.: R-7152 Paraffin Wax available from Moore & Munger in Shelton. Conn.: and Paraffin Wax 1297 available from International Waxes. Ltd in Ontario. Canada.
  • paraffinic waxes include waxes available from CP Hall under the product designations 1230, 1236, 1240, 1245, 1246, 1255, 1260, & 1262.
  • CP Hall 1246 paraffinic wax is available from CP Hall (Stow. Ohio).
  • CP Hall 1246 paraffinic wax has a melting point of 143°F (62°C), a viscosity at 210°F (99°C) of 4.2 centipoise (0.042 grams/(cm.second)), and a specific gravity at 73°F (23°C) of 0.915 g/cm 3 .
  • microcrystalline waxes useful here are those having 50 percent by weight or more cyclo or branched alkanes with a length of between 30 and 100 carbons. They are generally less crystalline than paraffin and polyethylene waves, and have melting points of greater than about 70°C Examples include Victory® Amber Wax, a 70°C melting point wax available from Petrolite Corp. located in Tulsa, Okla.; Bareco® ES-796 Amber Wax, a 70°C melting point wax available from Bareco in Chicago, III.; Okerin® 177, an 80°C melting point wax available from Astor Wax Corp.: Besquare® 175 and 195 Amber Waxes and 80°C and 90°C melting point microcrystalline waxes both available from Petrolite Corp. in Tulsa.
  • Indramic® 91 a 90°C melting point wax available from Industrial Raw Materials located in Smethport. Pa.: and Petrowax® 9508 Light, a 90°C melting point wax available from Petrowax PA. Inc. located in New York. N.Y.
  • the synthetic high melting point (HMP) waxes useful herein are high density, low molecular weight polyethylene waxes, by-product polyethylene waxes and Fischer-Tropsch waxes.
  • Preferred waxes include Petrolite® C-4040. Polywaxe® 1000, 2000 and 3000, low molecular weight polyethylene waxes available from Petrolite Corp.; Escomer® H-101, a modified polyethylene wax available from Exxon Chemical Co.: Marcus® 100. 200 and 300, low molecular weight by-product polyethylene waxes available from Marcu Chemical Co., a Division of H.R.D. Corp. located in Houston. Tex.; Paraflint® H-1, H-4 and H-8. Fischer-Tropsch waxes available from Sasol-SA/Moore & Munger in Shelton, Conn.: and Petrolite® PX-100, a Fischer-Tropsch wax available from Bareco.
  • Preferred waxes particularly when it is desired to prepare the hot melt adhesives of the invention in a dual reactor scheme, will be homogeneous waxes prepared using a constrained geometry or single site catalyst and using the procedures such as are set forth above and in the Examples below.
  • Such polymers will be either ethylene homopolymers or interpolymers of ethylene and a comonomer which is a C3-C20 ⁇ -olefin, styrene, alkylsubstituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, non-conjugated diene, or naphthenic, preferably a C4-C30 ⁇ -olefin or styrene, and more preferably, a C6-C20 ⁇ -olefin.
  • a comonomer which is a C3-C20 ⁇ -olefin, styrene, alkylsubstituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, non-conjugated diene, or naphthenic, preferably a C4-C30 ⁇ -olefin or styrene, and more
  • the homogeneous wax will have a melt viscosity at 350°F such as to yield the desired overall viscosity and close time of the hot melt adhesive formulation.
  • the homogeneous wax will have a melt viscosity at 350°F (177°C) of no more than 1000 centipoise (10 grams/(cm.second)), preferably no more than 800 centipoise (8 grams/(cm,second)), with homogeneous waxes having a melt viscosity at 350°F (177°C) of no more than 500 centipoise (5 grams/(cm.sccond)) being useful.
  • the homogeneous wax will typically have a melt viscosity at 350°F (177°C) of at least 100 centipoise (1 grams/(cm.second)), typically at least 120 centipoise (1.2 grams/(cm.second)), more typically at least 150 centipoise (1.5 grams/cm.second), with waxes having a melt viscosity at 350°F (177°C) of at least 200 centipoise (2 grams/(cm.second)) being particularly preferred from the standpoint of process economics.
  • Such polymers in contrast to traditional waxes, will preferably have a Mw/Mn of from 1.5 to 2.5. preferably from 1,8 to 2,2.
  • the homogeneous wax will have a density of at least 0.885 g/cm 3 , preferably at least 0.900 g/cm 3 , more preferably at least 0.920 g/cm 3 .
  • the homogeneous wax will have a density of no more than 0.970 g/cm 3 , preferably no more than 0.965 g/cm 3 , more preferably no more than 0.940 g/cm 3 ,
  • the waxes are useful in amounts from 0 percent to 40 percent by weight in the adhesive, preferably from 15 percent to 35 percent by weight in the adhesive and most preferably from 20 percent to 30 percent by weight in the adhesive, and may be used in any combination.
  • waxes are useful to modify the rate of set, lower the viscosity, increase the heat resistance and improve machineability of the finished adhesive.
  • the amount and type of wax used will be determined based on those factors.
  • the waxes mentioned above can also be combined with the polyhydroxyalkanoates of the present invention to provide biodegradable wax compositions according to the present invention, which are useful in many fields including protective films, layers and coatings for products such as food products, as described in more detail below.
  • tackifier means any of several hydrocarbon based compositions useful to impurt tack to the hot melt adhesive composition.
  • tackifiers include aliphatic C5 resins, polyterpene resins, hydrogenated resins, mixed aliphatic-aromatic resins, rosin esters, and hydrogenated rosin esters.
  • Exemplary tackifying resins useful herein include aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons and hydrogenated versions: terpenes and modified terpenes and hydrogenated versions: and rosins and rosin derivatives and hydrogenated versions; and mixtures thereof.
  • These tackifying resins have a ring and ball softening point from 70°C to 150°C, and will typically have a viscosity at 350°F (177°C), as measured using a Brookfield viscometer, of no more than 2000 centipoise (20 grams/cm,second). They are also available with differing levels or hydrogenation, or saturation, which is another commonly used term.
  • Useful examples include Eastotac® H-100, H-115 and H-130 from Eastman Chemical Co. in Kingsport, Tenn., which are partially hydrogenated cycloaliphatic petroleum hydrocarbon resins with softening points of 100°C. 115°C and 130°C, respectively. These are available in the E grade, the R grade, the L grade and the W grade, indicating differing levels of hydrogenation with E being the least hydrogenated and W being the most hydrogenated.
  • the E grade has a bromine number of 15.
  • the R grade a bromine number of 5
  • the L grade a bromine number of 3
  • the W grade has a bromine number of 1.
  • Eastotac® H-142R from Eastman Chemical Co. has a softening point of about 140°C.
  • tackifying resins include Escorez® 5300 and 5400. partially hydrogenated cycloaliphatic petroleum hydrocarbon resins, and Escorez® 5600. a partially hydrogenated aromatic modified petroleum hydrocarbon resin all available from Exxon Chemical Co. in Houston. Tex.: Wingtack® Extra which is an aliphatic, aromatic petroleum hydrocarbon resin available from Goodyear Chemical Co. in Akron. Ohio: Hercolite® 2100, a partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from Hercules. Inc. in Wilmington, Del.; and Zonatac® 105 and 501 Lite, which are styrenated terpene resins made from d-limonene and available from Arizona Chemical Co. in Panama City, Fla.
  • rosins and modified rosins available with differing levels of hydrogenation including gum rosins, wood rosins, tall-oil rosins, distilled rosins, dimerized rosins and polymerized rosins.
  • Some specific modified rosins include glycerol and pentaerythritol esters of wood rosins and tall-oil rosins.
  • Commercially available grades include, but are not limited to. Sylvatac® 1103, a pentaerythritol rosin ester available from Arizona Chemical Co.. Unitac® R-100 Lite, a pentaerythritol rosin ester from Union Camp in Wayne. N.J..
  • Permalyn® 305 a erythritol modified wood rosin available from Hercules and Foral 105 which is a highly hydrogenated pentacrythritol rosin ester also available from Hercules.
  • Sylvatac® R-85 and 295 are 85°C and 95°C melt point rosin acids available from Arizona Chemical Co.
  • Foral AX is a 70°C melt point hydrogenated rosin acid available from Hercules, Inc.
  • Nirez V-2040 is a phenolic modified terpene resin available from Arizona Chemical Co.
  • tackifiers that can be used according to embodiments of the present invention include alpha-methylstyrene resins and hydrogenated hydrocarbon resins that can contain aliphatic or aromatic hydrocarbons, for example, resins of these types available from Hercules. Inc.
  • Piccotac 115 Another exemplary tackifier that can be used according to the present invention is Piccotac 115. which has a viscosity at 350°F (177°C) of about 1600 centipoise (16 grams/(cm.second)). Other typical tackifiers have viscosities at 350°F (177°C) of much less than 1600 centipoise (16 grams/(cm.second)), for instance, from 50 to 300 centipoise (0.5 to 3 grams/(cm.second)).
  • Exemplary aliphatic resins include those available under the trade designations Escorez TM , Piccotac TM , Mercures TM , Wingtack TM , Hi-Rez TM , Quintone TM , Tackirol TM , etc.
  • Exemplary polyterpene resins include those available under the trade designations Nirez TM , Piccolyte TM , Wingtack TM , Zonarez TM , etc.
  • Exemplary hydrogenated resins include those available under the trade designations Escorez TM , Arkon TM , Clearon TM , etc.
  • Exemplary mixed aliphatic-aromatic resins include those available under the trade designations Escorez TM , Regalite TM , Hercures TM , AR TM , Imprez TM , Norsolene TM M. Marukarez TM , Arkon TM M, Quintone TM , etc.
  • Other tackifiers may be employed, provided they are compatible with the homogeneous linear or substantially linear ethylene/ ⁇ -olefin interpolymer and the wax.
  • the hot melt adhesive is prepared without the use of a tackifier or with a minimal quantity of tackifier.
  • tackifiers are malodorous, tend to cause corrosion of mechanical equipment, and cannot be easily separated from recycled paper pulp, hot melt adhesives which minimize the use of tackifiers are advantageous.
  • hot melt adhesives which minimize the use of tackifiers exhibit improved thermal stability.
  • Hot melt adhesives having less than about 20 weight percent tackifier, preferably less than about 15 weight percent tackifier and more preferably less than about 10 weight percent tackifier are preferred when preparing the hot melt adhesive in a dual reactor configuration.
  • the adhesive of the present invention contains tackifying resins present in an amount from about 10 percent to about 60 percent by weight in the adhesive, preferably from about 20 to about 55 percent by weight in the adhesive, more preferably from about 25 percent to about 50 percent by weight in the adhesive, and most preferably from about 30 percent to about 45 percent by weight in the adhesive.
  • Additives such as antioxidants (e.g., hindered phenolics (e.g., Irganox TM 1010, Irganox TM 1076), phosphites (e.g., Irgafos TM 168)), antiblock additives, pigments dyes, fluorescing agents, and fillers, can also be included in the modified formulations, to the extent that they do not interfere with the enhanced formulation properties.
  • antioxidants e.g., hindered phenolics (e.g., Irganox TM 1010, Irganox TM 1076), phosphites (e.g., Irgafos TM 168)
  • antiblock additives e.g., pigments dyes, fluorescing agents, and fillers
  • Stabilizer and antioxidants can be added to protect the adhesive from degradation caused by reactions with oxygen which are induced by such things as heat, light, or residual catalyst from the raw materials, Lowering the temperature of application as in the present invention also helps to reduce degradation.
  • Such antioxidants are commercially available from Ciba-Geigy located in Hawthorn. N.Y. and include Irganox® 565, 1010 and 1076 which are hindered phenolic antioxidants. These are primary antioxidants which act as free radical scavengers and may be used alone or in combination with other antioxidants such as phosphite antioxidants like Irgafos® 168 available from Ciba-Geigy.
  • Phosphite antioxidants are considered secondary antioxidants, are not generally used alone, and are primarily used as peroxide decomposers. Other available antioxidants are Cyanox® LTDP available from Cytec Industries in Stamford, Conn, and Ethanox® 1330 available from Albemarle Corp. in Baton Rouge. La, Many other antioxidants are available for use by themselves, or in combination with other such antioxidants. When employed, the antioxidant is typically present in an amount less than about 0.5 weight percent, preferably less than about 0.2 weight percent, based on the total weight of the hot melt adhesive.
  • the hot melt adhesive may further contain an oil.
  • Oils are typically present to reduce the viscosity of the hot melt adhesive. When present, oils are preferably present in an amount less than about 15 wt%, preferably less than about 10 wt%, and more preferably less than about 5 wt%, based on the weight of the hot melt adhesive.
  • Exemplary classes of oils include white mineral oil (such as Kaydol TM oil (available from Wilco). and Shellflex TM 371 naphlithenic oil (available from Shell Oil Company). To the extent that the oil decreases the adhesion character of the hot melt adhesive to levels detrimental for the contemplated use, it should not be used.
  • the hot melt adhesives of the invention may he prepared by standard melt blending procedures.
  • the homogeneous linear or substantially linear ethylene polymer, wax, and optional tackifier(s) may be melt blended at an elevated temperature (from 150 to 200°C) under an inert gas blanket until a homogeneous mix is obtained.
  • Any mixing method producing a homogeneous blend without degrading the hot melt components is satisfactory, such as through the use of a heated vessel equipped with a stirrer.
  • the first pylymer(s), wax(s), and the optional tackifier(s) may be used with an extrusion coater for application to the substrate.
  • the wax is a homogeneous wax
  • the reactors may be operated in series or in parallel.
  • hot melt adhesives can be provided in forms such as pellets, pillows, or any other desired configuration.
  • examples of such a process which may be adapted in accordance with the teachings of this disclosure to prepare blends of a homogenous linear (higher molecular weight or ultra-low molecular weight) or substantially linear ethylene/ ⁇ -olefin interpolymer, wax, and optional tackifier, are disclosed in WO 94/00500 and WO 94/01052 .
  • the resultant adhesives preferably have Brookfield TM viscosities of less than about 5.000 cps (50 grams/(cm.second)) at 150°C. preferably less than about 3.500 cps (35 grams/(cm.second)) at about 150°C and most preferably less than about 2.000 cps (20 grams/(cm.second)) at about 150°C making them ideally suited for application temperatures of less than about 150°C. and preferably from about 135°C to about 150°C on extrusion type packaging equipment, such as those manufactured by Nordson Corp. of Atlanta, Ga, Mercer Corp.. Slautterback Corp. and 1TW also manufacture extrusion type packaging equipment.
  • the hot melt adhesives of the present invention can be used for hot melt spray spray applications.
  • the hot melt adhesives of the present invention are further preferably characterized by excellent heat resistance and excellent flexibility.
  • the 100 gram peel values are an illustration of the heat resistance of the adhesive composition.
  • the peel values (PAFT) are preferably greater than about 40°C, more preferably greater than about 50°C and most preferably greater than about 60°C. High heat resistance in combination with good cold temperature properties is a significant improvement in the state of the art for low temperature packaging adhesives.
  • These hot melt adhesives are ideally suited for use in the packaging industry for case and carton sealing and for tray forming.
  • These packages may be manufactured from materials such as virgin and recycled kraft, high and low density kraft, chipboard and various types of treated and coated kraft and chipboard, and corrugated versions of these materials.
  • These adhesives may also bond composite materials such as those types of packages used for packaging of alcoholic beverages.
  • These composite materials may include chipboard laminated with an aluminum foil which is further laminated to film materials such as polyethylene, mylar, polypropylene, polyvinylidene chloride, ethylene vinyl acetate and various other types of films. Such film materials may also be bonded directly to chipboard or kraft in the absence of aluminum foil.
  • film materials may also be bonded directly to chipboard or kraft in the absence of aluminum foil.
  • the present invention also provides wax compositions containing the terminally-modified or low molecular weight polyhydroxyalkanoates.
  • the wax compositions include a polyhydroxyalkanoate selected from: biodegradable polyhydroxyalkanoates having a molecular weight of from about 500 to less than 50,000; and biodegradable polyhydroxyalkanoates having at least one of the terminal end groups selected from:
  • the wax compositions of the present invention can preferably further include at least one other component selected from paraffin waxes, microcrystalline waxes, high density low molecular weight polyethylene waxes, by-product polyethylene waxes. Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxy stearamide waxes, fatty amide waxes, and combinations thereof. Other waxes and additives as described above with reference to the hot melt adhesive applications can also be used in the wax compositions of the present invention.
  • the wax compositions of the present invention can be made into layers, coatings or films that are useful as protective coatings for articles. Layers, coatings and films consisting essentially of the wax compositions of the present invention are within the realm of the present invention. Articles having a protective coating thereon, wherein the protective coating includes or consists essentially of the wax composition of the present invention are also provided by the present invention.
  • the wax compositions of the present invention can also include a pigment or dye.
  • Food safe pigments or dyes are preferred for uses such as coating food products, and are known to those skilled in the art.
  • Food products having a protective coating on a surface thereof, that includes the wax compositions of the present invention are also within the realm of the present invention.
  • the wax compositions of the present invention are particularly well suited for encapsulating food products to protect the food products, for example, as coatings for cheese products. In this regard, methods of protecting articles, including food products such as cheese products, are also included in accordance with embodiments of the present invention.
  • a first protective layer of a biologically degradable hydrophobic polyhydroxyalkanoate can be coated onto the surface of the food product, such as cheese, from an aqueous dispersion or latex composition. Such a coating can be used to control the gas and moisture transmission properties out of the product.
  • the hydrophobic polyhydroxyalkanoate allows the cheese to mature over a period of time.
  • the maturation process can be terminated by application of a paraffin wax coating or, more preferably, a second polyhydroxyalkanoate coating applied to the surface of the dried latex applied polyhydroxyalkanoate coating.
  • the second coating preferably terminates the maturation process and preferably provides a totally moisture and gas impervious barrier and a coating more resistant to mechanical damage.
  • the coating temperature for applying the second coating of polyhydroxyalkanoate is preferably carried out at a temperature at which the second polyhydroxyalkanoate material. e.g., oligomer, is more molten, preferably in the range of from about 40 °C to about 90 °C. More preferably, the glass transition temperature of the latex polyhydroxyalkanoate coating does not differ by more than about 20°C from the glass transition temperature of the molten-applied second polyhydroxyalkanoate coating. More preferably, the glass transition temperature of the latex polyhydroxyalkanoate coating is in the range of from about 0 °C to about 35°C.
  • the molecular weight of the molten-applied polyhydroxyalkanoate should be less than that of the polyhydroxyalkanoate latex polymer and preferably should differ by a number average molecular weight of more than about 10,000, and more preferably, more than about 50.000.
  • a method for producing a biologically degradable polyhydroxyalkanoate coating in the form of an elastomeric film is also provided according to the present invention.
  • the method involves forming an aqueous dispersion of the low molecular weight or terminally modified polyhydroxyalkanoate. The dispersion is applied to the surface to be coated. Afterwards, the water is made or allowed to evaporate to obtain a film, wherein the film formation taking place at a temperature lower than the melting point of the polyhydroxyalkanoate.
  • the method for producing a coating in the form of an elastomeric film according to the invention does not require further steps of hot fusion, hot pressing, or contact with chloroform or halogenated solvent to obtain the elastomeric characteristic.
  • the method according to the invention can be carried out at a temperature more than about 35°C lower than the melting point of the polyhydroxyalkanoate.
  • a polymer is used that has such low melting points, glass transition temperatures, and crystallinity that the film formation takes place at a temperature lower than the melting point of the polyhydroxyalkanoates and can even occur at a temperature more than about 35°C below the melting temperature.
  • the processing of PHA to form a coating can be carried out just by applying the dispersion and by allowing it to dry.
  • the polyhydroxyalkanoates of the PHB type probably do not form an impermeable film because of the high crystallinity and the high glass transition temperature of about 0-4°C.
  • the polyhydroxyalkanoate preferably has a glass transition temperature below about 0°C.
  • a method for making a hot melt adhesive by combining a polyhydroxyalkanoate as a latex with a resin emulsion or a wax emulsion and spray drying the blend to make a hot melt adhesive without the need for a hot melt compounding process.
  • a high-temperature step is unnecessary for sintering or melting for the purpose of film formation.
  • Neither the presence of an organic solvent nor an intermediate step in which the aqueous dispersion of PHA is dried to form a powder and then dissolved in an organic solvent is necessary.
  • the coating does not per se need, however, to be applied to or consumed by the animal or the human being.
  • the method according to the present invention can be performed at a temperature in the range of about 0-30°C, preferably at a temperature in the range of about 10-18°C.
  • the choice of temperature employed will depend on the product to be coated and on economic considerations.
  • the PHA used will also be a factor on which the temperature to be used depends.
  • the method according to the invention can be performed with good results using a dispersion whose dry-matter content of PHA is at least about 10%. Outstanding results arc achieved with a dry-matter content higher than about 30% and even higher than about 50%. Dispersions with a dry matter content higher than about 65% have been shown to be suitable embodiments for use in preparing elastomeric films according to the invention.
  • the dispersions preferably having a pH higher than about 8, preferably higher than about 10, Suitably the p11 is about 12 as illustrated in the Examples.
  • a dispersion according to the invention may further comprise more than about 30%, preferably more than about 50%, in particular more than about 65% polyhydroxyalkanoate as dry weight.
  • an aqueous latex-like dispersion according to any of the aforementioned embodiments is substantially free of compounds toxic to a human being or animal.
  • dispersions An advantage of the use of dispersions is that standard additives such as stabilizers, plasticizers, fillers, dyes, emulsifiers, thickening agents, antioxidants, antistatics, preservatives, crosslinking agents, etc. can be added to the dispersion and the properties of the film can be simply improved and modified thereby.
  • the presence of the water phase offers the possibility of mixing the PHA with other water-soluble, biologically degradable polymers.
  • Other biologically degradable polymers which can be taken up in the dispersion comprise polyvinyl alcohol, gelatin, methylcellulose, polyethene oxide. PVP, starch.
  • an anti-fungal agent can be taken up in the dispersion.
  • the method according to the present invention can advantageously be used to coat foodstuffs, in particular, for coating cheese.
  • the film which is obtained by the present method is outstandingly suitable for coating cheese. All the requirements which are imposed thereon with respect to suitable cheese coatings are fulfilled by the coatings of the present invention.
  • the mechanical strength of the coating is a positive factor.
  • the film obtained resembles a "latex" film.
  • a drying time of less than about 24 hours at an atmospheric humidity of about 85% and a temperature of about 10-18°C may be adequate.
  • This method according to the invention is outstandingly suitable for producing a cheese coating.
  • the present invention also relates to a product coated with a polyhydroxyalkanoate film according to the present invention.
  • a coated product according to the invention can be a product to be applied to or consumed by a human being or animal or a product which must not be exposed to about 100°C or more.
  • a suitable product is cheese.
  • the product coated with polyhydroxyalkanoate film may also be composed of a mixture of polyhydroxyalkanoates of the above-mentioned type.
  • the invention also relates to products coated with polyhydroxyalkanoate film of the above type which can be prepared by the method according to the invention.
  • a film according to the invention is water resistant.
  • the invention relates to an elastomeric film of polyhydroxyalkanoate which is suitable as a coating for products suitably to be applied to or consumed by human beings and/or animals.
  • the film according to the invention can suitably be applied to a hydrophilic surface and exhibits good attachment properties to such a surface without requiring a heating step or any other step than drying at a temperature below T m (melting temperature). In fact temperatures more than about 35°C below T m can even be applied.
  • Cheese is a suitable product.
  • a preferred film according to the present invention has an elongation at break of at least about 50%. Preferably, the elongation at break is over 200%.
  • the dry-matter content of a film according to the invention can be more than about 10%, and preferably higher than about 30%, more preferably higher than about 50%.
  • Another property of a a film suitable in cheese coatings is a film containing less than about 4.5% of parts which are soluble in water.
  • the typical gas permeability is 3-5 l/m 2 /hr at a temperature of about 20°C and relative humidity of 90-0% for a film according to the invention. These values being for a film with a thickness of about 0.1 mm.
  • the present invention is also directed to the lattices useful for the production of such films as can be produced in the various embodiments of the preparation method of coated products according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Food Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Dairy Products (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (28)

  1. Composition de polyhydroxyalcanoate comprenant au moins un polyhydroxyalcanoate biodégradable ayant une masse moléculaire moyenne en nombre de 500 à moins de 50 000 et comprenant en outre au moins un composant monomère réactif, dans laquelle ledit monomère réactif est au moins l'un parmi un monomère époxy, un monomère acrylate, un monomère méthacrylate, un monomère silicone, un monomère siloxane, un monomère uréthane, un monomère isocyanate, un monomère anhydride, une oxime, un monomère époxy novolaque, un monomère époxy bisphénol A, un monomère silane et leurs combinaisons, le polyhydroxyalcanoate comprenant un polymère choisi dans l'ensemble constitué par les polymères de 3-hydroxyacides, de 4-hydroxyacides, de 5-hydroxyacides, leurs copolymères, et leurs mélanges.
  2. Composition de polyhydroxyalcanoate selon la revendication 1, dans laquelle la masse moléculaire est d'environ 1 000 à environ 5 000.
  3. Composition de polyhydroxyalcanoate selon la revendication 1, dans laquelle la masse moléculaire est d'environ 1 000 à environ 3 000.
  4. Composition de polyhydroxyalcanoate selon la revendication 1, dans laquelle le polyhydroxyalcanoate comprend un polymère d'une ou plusieurs sous-unités ayant la formule chimique :

            T- [-OCR1R2(CR3R4)nCO) -]p-Q

    dans laquelle n vaut 0 ou est un entier allant jusqu'à environ 100 ; p vaut jusqu' à 100 ; chacun de R1, R2, R3 et R4 qui sont identiques les uns aux autres ou différents les uns des autres, est indépendamment choisi parmi les radicaux hydrocarbonés saturés et insaturés, les radicaux halogéno- et hydroxy-substitués, les radicaux hydroxy, les radicaux halogéno, les radicaux azote-substitués, les radicaux oxygène-substitués et les atomes d'hydrogène ; T est choisi parmi l'hydrogène, les groupes alkyle, aryle, alcaryle et aralkyle contenant d'environ 1 à environ 20 atomes de carbone, et un groupe carboxylate R"'COO où R"' est un radical hydrocarboné aliphatique ou aromatique contenant d'environ 1 à environ 20 atomes de carbone ; et Q est choisi parmi :
    un radical hydroxy ou un radical OR" où R" est un radical alkyle, aryle, alcaryle ou aralkyle substitué ou non substitué contenant de 1 à environ 20 atomes de carbone ;

            OAOH ;

    OAOOC (CH2)yCHROH ; ou OAO{OC(CH2)yCHRO}xH; où chaque R est indépendamment choisi parmi l'hydrogène, un groupe alkyle saturé ayant d'environ 1 à environ 16 atomes de carbone,
    un groupe alkyle insaturé ayant d'environ 2 à environ 16 atomes de carbone ; et leurs mélanges ; A est (CH2)m ou (CH2CHR'O)m où m vaut d'environ 1 à environ 50 et R' est l'hydrogène ou méthyle ; x vaut d'environ 2 à environ 50 ;
    y vaut de 0 à environ 3 ; et
    dans laquelle la masse moléculaire moyenne en nombre du composé est d'au moins 500.
  5. Composition de polyhydroxyalcanoate selon la revendication 1, dans laquelle le polyhydroxyalcanoate est choisi parmi le poly(hydroxybutyrate), le copoly(hydroxybutyrate/hydroxyvalérate), le copoly(hydroxybutyrate/4-hydroxybutyrate), le copoly(hydroxybutyrate/3-hydroxyhexanoate), le copoly(hydroxybutyrate/3-hydroxyheptanoate), et le copoly(hydroxybutyrate/3-hydroxyoctanoate).
  6. Composition de polyhydroxyalcanoate selon la revendication 1, dans laquelle le polyhydroxyalcanoate comprend un mélange de polyhydroxyalcanoates thermiquement dépolymérisables.
  7. Composition de polyhydroxyalcanoate selon la revendication 1, comprenant en outre au moins un polymère thermiquement dépolymérisable autre que le polyhydroxyalcanoate.
  8. Composition de polyhydroxyalcanoate selon la revendication 7, dans laquelle le polymère thermiquement dépolymérisable est choisi parmi les polycarbonates, les polyoléfines, les polystyrènes, les polyacétals, les cires, et leurs combinaisons.
  9. Composition de polyhydroxyalcanoate selon la revendication 1, dans laquelle le polyhydroxyalcanoate est dissous dans un solvant ou un mélange de solvants.
  10. Composition de polyhydroxyalcanoate selon la revendication 1, laquelle composition de polyhydroxyalcanoate est biodégradable.
  11. Composition adhésive thermofusible comprenant :
    au moins un polyhydroxyalcanoate biodégradable ayant une masse moléculaire moyenne en nombre de 500 à moins de 50 000 ;
    comprenant éventuellement au moins une résine donnant du collant ; et
    comprenant éventuellement au moins une cire ;
    laquelle composition adhésive thermofusible a une viscosité inférieure à environ 100 000 centipoises à 150°C, et comprend en outre au moins un composant monomère réactif, ledit monomère réactif étant au moins l'un parmi un monomère époxy, un monomère acrylate, un monomère méthacrylate, un monomère silicone, un monomère siloxane, un monomère uréthane, un monomère isocyanate, un monomère anhydride, une oxime, un monomère époxy novolaque, un monomère époxy bisphénol A, un monomère silane et leurs combinaisons,
    le polyhydroxyalcanoate comprenant un polymère choisi dans l'ensemble constitué par les polymères de 3-hydroxyacides, de 4-hydroxyacides, de 5-hydroxyacides, leurs copolymères, et leurs mélanges.
  12. Composition adhésive thermofusible selon la revendication 11, dans laquelle ladite au moins une résine donnant du collant est présente dans ladite composition.
  13. Composition adhésive thermofusible selon la revendication 11, dans laquelle ladite au moins une résine donnant du collant est présente dans ladite composition en une quantité allant jusqu'à environ 60 % en poids par rapport au poids total de la composition.
  14. Composition adhésive thermofusible selon la revendication 11, dans laquelle ladite au moins une cire est présente dans ladite composition.
  15. Composition adhésive thermofusible selon la revendication 11, dans laquelle ladite au moins une cire est présente dans ladite composition en une quantité allant jusqu'à environ 40 % en poids par rapport au poids total de la composition.
  16. Composition adhésive thermofusible selon la revendication 11, dans laquelle la masse moléculaire est d'environ 1 000 à environ 5 000, de préférence d'environ 1 000 à environ 3 000.
  17. Composition adhésive thermofusible selon la revendication 11, dans laquelle le polyhydroxyalcanoate comprend un polymère d'une ou plusieurs sous-unités ayant la formule chimique :

            T-[-OCR1R2(CR3R4)nCO)-]p-Q

    dans laquelle n vaut 0 ou est un entier allant jusqu'à environ 100 ; p vaut jusqu' à 100 ; chacun de R1, R2, R3 et R4 qui sont identiques les uns aux autres ou différents les uns des autres, est indépendamment choisi parmi les radicaux hydrocarbonés saturés et insaturés, les radicaux halogéno- et hydroxy-substitués, les radicaux hydroxy, les radicaux halogéno, les radicaux azote-substitués, les radicaux oxygène-substitués et les atomes d'hydrogène ; T est choisi parmi l'hydrogène, les groupes alkyle, aryle, alcaryle et aralkyle contenant d'environ 1 à environ 20 atomes de carbone, et un groupe carboxylate R"'COO où R"' est un radical hydrocarboné aliphatique ou aromatique contenant d'environ 1 à environ 20 atomes de carbone ; et Q est choisi parmi :
    un radical hydroxy ou un radical OR" où R" est un radical alkyle, aryle, alcaryle ou aralkyle substitué ou non substitué contenant de 1 à environ 20 atomes de carbone ;

            OAOH ;

            OAOOC (CH2)yCHROH ;

    ou

            OAO {OC (CH2)yCHRO}xH;

    où chaque R est indépendamment choisi parmi l'hydrogène, un groupe alkyle saturé ayant d'environ 1 à environ 16 atomes de carbone, un groupe alkyle insaturé ayant d'environ 2 à environ 16 atomes de carbone, et leurs mélanges ; A est (CH2)m ou (CH2CHR'O)m où m vaut d'environ 1 à environ 50 et R' est l'hydrogène ou méthyle ; x vaut d'environ 2 à environ 50 ; y vaut de 0 à environ 3 ; et dans laquelle la masse moléculaire moyenne en nombre du composé est d'au moins 500.
  18. Composition adhésive thermofusible selon la revendication 11, dans laquelle le polyhydroxyalcanoate est choisi parmi le poly(hydroxybutyrate), le copoly-(hydroxybutyrate/hydroxyvalérate), le copoly(hydroxybutyrate/4-hydroxybutyrate), le copoly(hydroxybutyrate/3-hydroxyhexanoate), le copoly(hydroxybutyrate/3-hydroxyheptanoate), et le copoly(hydroxybutyrate/3-hydroxyoctanoate).
  19. Composition adhésive thermofusible selon la revendication 12.
  20. Composition adhésive thermofusible selon la revendication 11, dans laquelle le polyhydroxyalcanoate comprend un mélange de polyhydroxyalcanoates thermiquement dépolymérisables.
  21. Composition adhésive thermofusible selon la revendication 11, comprenant en outre au moins un polymère thermiquement dépolymérisable autre que le polyhydroxyalcanoate.
  22. Composition adhésive thermofusible selon la revendication 21, dans laquelle le polymère thermiquement dépolymérisable est choisi parmi les polycarbonates, les polyoléfines, les polystyrènes, les polyacétals, les cires, et leurs combinaisons.
  23. Composition adhésive thermofusible selon la revendication 11, dans laquelle le polyhydroxyalcanoate est dissous dans un solvant ou un mélange de solvants.
  24. Composition adhésive thermofusible selon la revendication 11, laquelle composition adhésive thermofusible est biodégradable.
  25. Article comprenant deux composants collés ensemble par la composition adhésive thermofusible de la revendication 11.
  26. Article comprenant deux composants ayant chacun une surface respective, les surfaces respectives des deux composants étant collées ensemble avec la composition adhésive thermofusible de la revendication 11.
  27. Procédé pour faire adhérer deux composants ensemble comprenant les étapes consistant à :
    se procurer deux composants ; et
    appliquer la composition adhésive thermofusible de la revendication 11 auxdits deux composants pour faire adhérer ensemble les deux composants.
  28. Procédé pour faire adhérer deux composants ensemble comprenant les étapes consistant à :
    se procurer deux composants ;
    appliquer la composition adhésive thermofusible de la revendication 11 à au moins l'un desdits deux composants ; et
    mettre en contact l'un desdits deux composants avec l'autre desdits deux composants de façon que ladite composition adhésive thermofusible se trouve entre lesdits deux composants.
EP01988751A 2000-10-27 2001-10-25 Compositions contenant des polyhydroxyalcanoates et des monomères réactifs Expired - Lifetime EP1330503B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US24381800P 2000-10-27 2000-10-27
US243818P 2000-10-27
PCT/US2001/045507 WO2002034857A2 (fr) 2000-10-27 2001-10-25 Compositions contenant des polyhydroxyalcanoates de faible poids moleculaire et procedes d'utilisation de celles-ci

Publications (2)

Publication Number Publication Date
EP1330503A2 EP1330503A2 (fr) 2003-07-30
EP1330503B1 true EP1330503B1 (fr) 2011-05-25

Family

ID=22920254

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01988751A Expired - Lifetime EP1330503B1 (fr) 2000-10-27 2001-10-25 Compositions contenant des polyhydroxyalcanoates et des monomères réactifs

Country Status (7)

Country Link
US (2) US7094840B2 (fr)
EP (1) EP1330503B1 (fr)
JP (1) JP2004512419A (fr)
AT (1) ATE510898T1 (fr)
AU (1) AU2002225827A1 (fr)
ES (1) ES2362405T3 (fr)
WO (1) WO2002034857A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9359283B2 (en) 2012-05-31 2016-06-07 Micromidas, Inc. Polyhydroxyalkanoate derivatives, preparation and uses thereof

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60336757D1 (de) * 2002-09-12 2011-05-26 Metabolix Inc Produktion von polyhydroxyalkanoat mittels coenzym-a-abhängiger aldehyd-dehydrogenase-wege
US7781539B2 (en) * 2003-02-21 2010-08-24 Metabolix Inc. PHA blends
ATE518932T1 (de) 2003-02-21 2011-08-15 Metabolix Inc Pha-mischungen
EP1693416B1 (fr) * 2003-12-02 2010-10-20 Kaneka Corporation Composition de poly(3-hydroxyalcanoate) et objet moule comprenant cette composition
EP1964879B1 (fr) * 2003-12-30 2012-06-13 Metabolix, Inc. Agents de nucléation
BRPI0502935B1 (pt) 2005-07-08 2016-11-16 Ioto Internat Indústria E Comércio De Produtos Aromáticos Ltda “composto aglutinante para a reconstituição de pó de origem vegetal tais como pós residuais da indústria de tabaco e de alimentos e respectivo produto aglutinado”
WO2007030791A1 (fr) * 2005-09-08 2007-03-15 Dow Global Technologies Inc. Adhesifs thermofusibles a base de polyester-amide
EP1917862B1 (fr) * 2006-10-19 2018-11-21 CSK Food Enrichment B.V. Enrobages pour aliments, en particulier pour fromage
DE102007046600A1 (de) * 2007-09-27 2009-04-02 Linhardt Metallwarenfabrik Gmbh & Co Kg Verfahren zum Applizieren eines flüssigen, medizinischen Behandlungsmediums auf einen zu behandelden Bereich sowie Medizinprodukt
TW201012846A (en) 2008-06-25 2010-04-01 Metabolix Inc Methods for branching PHA using thermolysis
CA2745223A1 (fr) * 2008-12-02 2010-06-10 Metabolix, Inc. Fabrication de mousse de polyhydroxyalcanoate
FR2942963B1 (fr) * 2009-03-11 2011-04-22 Oreal Composition cosmetique comprenant une matiere colorante, ladite matiere colorante et procede de traitement cosmetique
FR2952061B1 (fr) * 2009-10-30 2012-02-10 Valagro Carbone Renouvelable Poitou Charentes Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus
US8002399B2 (en) * 2009-12-02 2011-08-23 Xerox Corporation Solid inks incorporating a polyhydroxyalkanoate compound for enhanced properties
TWI453231B (zh) * 2010-11-22 2014-09-21 Univ Yuan Ze Biodegradability of Small Molecules and Its Use
US20110319849A1 (en) * 2011-07-01 2011-12-29 Dimitris Ioannis Collias Absorbent article comprising a synthetic polymer derived from a renewable resource and methods of producing said article
JP5983621B2 (ja) * 2011-09-27 2016-09-06 日本電気株式会社 バイオプラスチック成形体及びバイオプラスチック成形体の製造方法
EP3424990B1 (fr) 2012-06-05 2021-05-05 CJ CheilJedang Corporation Mélanges de polymères biodégradables
CN109054254B (zh) 2012-08-17 2021-02-02 Cj第一制糖株式会社 用于聚合物共混物的生物基橡胶改性剂
US9279061B2 (en) * 2012-09-12 2016-03-08 Xerox Corporation Phase change ink with compostable wax
WO2014078720A1 (fr) * 2012-11-15 2014-05-22 Rusi Taleyarkhan Compositions d'adhésif à base de poly(acide lactique) et procédés pour les préparer et les utiliser
EP2948513B1 (fr) * 2013-01-24 2019-08-07 Henkel IP & Holding GmbH Adhésif thermofusible réactif
JP6172795B2 (ja) * 2013-05-27 2017-08-02 国立研究開発法人理化学研究所 ポリエステル樹脂組成物およびその製造方法、並びに該樹脂組成物から形成される成形体
US10669417B2 (en) 2013-05-30 2020-06-02 Cj Cheiljedang Corporation Recyclate blends
JP6088929B2 (ja) * 2013-07-12 2017-03-01 出光ライオンコンポジット株式会社 熱可塑性樹脂組成物および成形品
WO2015149029A1 (fr) 2014-03-27 2015-10-01 Metabolix, Inc. Systèmes polymères fortement chargés
NL2014860B1 (en) * 2015-05-27 2017-01-31 Csk Food Enrichment Bv Cheese coating.
NL2014862B1 (en) 2015-05-27 2017-01-31 Csk Food Enrichment Bv Cheese coating.
EP3377579A1 (fr) 2015-11-17 2018-09-26 CJ Cheiljedang Corporation Mélanges polymères à vitesses de biodégradation pouvant être régulées
CA3017501A1 (fr) * 2016-03-11 2017-09-14 Snp, Inc. Procede de sechage a haute energie pour former un film polyhydroxyalcanoate continu
US10040894B2 (en) 2016-03-28 2018-08-07 International Business Machines Corporation Polymeric materials formed from polyhydroxyalkanoate materials
WO2018007548A1 (fr) 2016-07-07 2018-01-11 Repsol, S.A. Compositions de polyhydroxyalcanoates et de polymères polaires
WO2018070492A1 (fr) 2016-10-13 2018-04-19 株式会社カネカ Procédé de production d'acide polyhydroxyalcanoïque
US10072120B2 (en) 2016-12-02 2018-09-11 International Business Machines Corporation Functionalized polyhydroxyalkanoate materials formed from an unsaturated polyhydroxyalkanoate material
US10081706B2 (en) 2017-01-03 2018-09-25 International Business Machines Corporation Side-chain-functionalized polyhydroxyalkanoate materials
GB201718470D0 (en) * 2017-11-08 2017-12-20 Provost Fellows Found Scholars And The Other Members Of Board Of The College Of The Holy And Undivid Adhesive formulations
KR102318930B1 (ko) * 2017-12-18 2021-10-27 주식회사 엘지화학 폴리하이드록시알카노에이트를 포함하는 접착제 조성물
KR20210044812A (ko) * 2018-08-13 2021-04-23 데니머 바이오플라스틱스 인코포레이티드 수성 pha 분산물에 기반하는 생분해성 코팅
JP7209434B2 (ja) * 2019-10-31 2023-01-20 株式会社カネカ ポリヒドロキシアルカン酸の製造方法およびその利用
JPWO2021153250A1 (fr) 2020-01-29 2021-08-05
JPWO2023008298A1 (fr) * 2021-07-26 2023-02-02
KR20230143274A (ko) * 2022-04-05 2023-10-12 이창훈 차선규제봉에 사용되는 생분해성 성형체용 조성물

Family Cites Families (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2948023A1 (de) 1979-11-29 1981-06-04 Bayer Ag, 5090 Leverkusen (beta)-hydroxibuttersaeure-polyester, verfahren zu ihrer herstellung und ihre verwendung als lackrohstoffe
FR2486072A1 (fr) 1980-07-03 1982-01-08 Solvay Procede pour la fabrication de l'acide b-hydroxybutyrique et de ses oligocondensats
EP0145233B2 (fr) 1983-11-23 1991-11-06 Imperial Chemical Industries Plc Procédé de séparationpour un polymerede butyrate-3-hydroxy
AU603076B2 (en) 1985-12-09 1990-11-08 W.R. Grace & Co.-Conn. Polymeric products and their manufacture
US5245023A (en) 1987-06-29 1993-09-14 Massachusetts Institute Of Technology Method for producing novel polyester biopolymers
US5480794A (en) 1987-06-29 1996-01-02 Massachusetts Institute Of Technology And Metabolix, Inc. Overproduction and purification of soluble PHA synthase
US5250430A (en) 1987-06-29 1993-10-05 Massachusetts Institute Of Technology Polyhydroxyalkanoate polymerase
US5229279A (en) 1987-06-29 1993-07-20 Massachusetts Institute Of Technology Method for producing novel polyester biopolymers
US4876331A (en) 1987-08-18 1989-10-24 Mitsubishi Kasei Corporation Copolyester and process for producing the same
AT390068B (de) 1988-07-07 1990-03-12 Danubia Petrochemie Extraktionsmittel fuer poly-d(-)-3-hydroxybuttersaeure
US5444113A (en) * 1988-08-08 1995-08-22 Ecopol, Llc End use applications of biodegradable polymers
JPH0776332B2 (ja) 1988-11-18 1995-08-16 サンスター技研株式会社 湿気硬化性ホットメルト型接着剤組成物
FR2641532B1 (fr) 1989-01-06 1991-03-29 Solvay Procede pour la preparation d'esters de l'acide (beta)-hydroxybutyrique
US6090790A (en) * 1989-12-14 2000-07-18 Eriksson; Elof Gene delivery by microneedle injection
ATE115973T1 (de) 1990-03-30 1995-01-15 Fuller H B Licensing Financ Wasserhärtbarer polyurethanheissschmelzklebstoff.
AT395319B (de) 1990-10-05 1992-11-25 Danubia Petrochem Polymere Verfahren zur gewinnung eines polyhydroxyalkanoates aus dem zellmaterial eines mikroorganismus und polyhydroxyalkanoatflocken
US5286842A (en) 1991-07-01 1994-02-15 Mitsubishi Kasei Corporation Process for producing a biodegradable polymer
JP2777757B2 (ja) 1991-09-17 1998-07-23 鐘淵化学工業株式会社 共重合体およびその製造方法
JP2884123B2 (ja) 1992-01-17 1999-04-19 高砂香料工業株式会社 生分解性光学活性ポリマー、その中間体オリゴマー、およびそれらの製造方法
US5169889A (en) 1992-01-27 1992-12-08 National Starch And Chemical Investment Holding Corporation Poly hydroxybutyrate/hydroxyvalerate based hot melt adhesive
FI90502C (fi) * 1992-03-19 1994-02-25 Kemira Oy Platinaa säästävä katalyytti ja menetelmä sen valmistamiseksi
GB9223351D0 (en) * 1992-11-06 1992-12-23 Ici Plc Polyesters
JP3263710B2 (ja) 1992-12-11 2002-03-11 高砂香料工業株式会社 生分解性光学活性ポリマー及びその製造方法
GB9314577D0 (en) * 1993-07-14 1993-08-25 Zeneca Ltd Adhesion process
JP3241505B2 (ja) 1993-08-11 2001-12-25 高砂香料工業株式会社 生分解性光学活性コポリマー及びその製造方法
EP0723572B1 (fr) * 1993-10-15 1999-12-08 H.B. Fuller Licensing & Financing, Inc. Adhesifs thermofusibles biodegradables/recyclables en compost constitues de polyester d'acide lactique
WO1995018781A1 (fr) 1994-01-06 1995-07-13 Metabolix, Inc. Procedes de synthese d'oligomeres contenant des unites d'acide hydroxylique
ZA95627B (en) * 1994-01-28 1995-10-05 Procter & Gamble Biodegradable copolymers and plastic articles comprising biodegradable copolymers
US5685756A (en) * 1994-01-28 1997-11-11 The Procter & Gamble Company Nonwoven materials comprising biodegradable copolymers
CN1070203C (zh) * 1994-01-28 2001-08-29 普罗克特和甘保尔公司 由烷氧基烷基锌引发的β－取代的β－丙内酯的聚合方法
AU703156B2 (en) * 1994-01-28 1999-03-18 Procter & Gamble Company, The Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate
US5466780A (en) * 1994-03-30 1995-11-14 Exxon Chemical Patents Inc. Process for converting polyketones to polyesters
DE59508729D1 (de) 1994-08-10 2000-10-26 Peter Neuenschwander Biokompatibles Blockcopolymer
DE69515044T2 (de) * 1994-08-12 2000-06-08 Minnesota Mining & Mfg Poly(beta-hydroxyorganoat)haftklebstoffzusammensetzungen
DE4433987A1 (de) 1994-09-23 1996-03-28 Muehlbauer Ernst Kg Polymerisierbare Oligo- und/oder Polyalkensäuren
US6008184A (en) 1994-09-30 1999-12-28 The Procter & Gamble Company Block copolymers for improved viscosity stability in concentrated fabric softeners
US5563239A (en) 1994-11-09 1996-10-08 Eastman Chemical Company Composition and process for the production of poly(3-hydroxyalkanoates)
US5583187A (en) 1995-05-03 1996-12-10 National Starch And Chemical Investment Holding Corporation Hot melt adhesives based on hydroxy-functional polyesters
US5574076A (en) * 1995-05-03 1996-11-12 National Starch And Chemical Investment Holding Corporation Sucrose benzoate as a tackifier for water sensitive or biodegradable hot melt adhesives
US5852078A (en) * 1996-02-28 1998-12-22 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester compositions with natural polymers and articles thereof
EP0937112A1 (fr) 1996-11-08 1999-08-25 Imperial Chemical Industries Plc Procede de fabrication de mousses rigides ou souples de polyurethane
JPH10261301A (ja) * 1997-01-16 1998-09-29 Honda Motor Co Ltd 車両用前照灯
AU710285B2 (en) 1997-03-27 1999-09-16 Kyowa Yuka Co., Ltd. Polyurethanes and polyester polyol
DE69837917T2 (de) * 1997-04-21 2008-02-21 Metabolix, Inc., Cambridge Endstellige hydroxyl aufweisende polyhydroxyalkanoate
US6156852A (en) * 1997-04-21 2000-12-05 Monsanto Company Hydroxy-terminated polyhydroxyalkanoates
DE19718018A1 (de) 1997-04-29 1998-11-05 Basf Ag Verfahren zur Herstellung von Polyurethan-Hartschaumstoffen
US5900473A (en) 1997-06-16 1999-05-04 H.B. Fuller Licensing & Financing, Inc. Radiation curable pressure sensitive adhesives
WO1999002587A1 (fr) 1997-07-09 1999-01-21 Huntsman Ici Chemicals Llc Mousses comprimees hydrophiles de polyurethanne
WO1999005209A1 (fr) 1997-07-22 1999-02-04 Metabolix, Inc. Compositions de moulage de polyhydroxyalcanoate
ATE328035T1 (de) * 1997-07-25 2006-06-15 Metabolix Inc Pha-zusammensetzungen und deren verwendung zur herstellung von pha-filmen
US5952405A (en) 1997-08-26 1999-09-14 National Starch And Chemical Investment Holding Corporation Lactide graft copolymers and hot melt adhesives prepared from same
AU9396898A (en) * 1997-09-18 1999-04-05 Monsanto Company Modified polyhydroxyalkanoates for production of coatings and films
DE19741257A1 (de) 1997-09-19 1999-03-25 Basf Ag Verfahren zur Herstellung von Polyurethanschaumstoffen
US5939488A (en) 1997-10-15 1999-08-17 National Starch And Chemical Investment Holding Corporation Fast setting polyurethane hot melt adhesive composition comprising low hydroxyl number/high molecular weight polyester diols
WO1999023146A1 (fr) * 1997-10-31 1999-05-14 Monsanto Company Compositions de polyhydroxyalcanoates et leurs procedes d'utilisation dans la production de pieces moulees polymeres
KR100515274B1 (ko) * 1997-11-14 2005-09-15 미쓰비시 쥬시 가부시끼가이샤 생분해성 필름 및 그 제조방법
ES2356350T3 (es) 1997-12-22 2011-04-07 Metabolix, Inc. Composiciones polihidroxialcanoato que tienen tasas de degradación controladas.
US6174990B1 (en) * 1998-12-21 2001-01-16 The Procter & Gamble Company Films comprising biodegradable PHA copolymers
US6479145B1 (en) * 1999-09-09 2002-11-12 Regents Of The University Of Minnesota Biopolymers and biopolymer blends, and method for producing same
JP2003535935A (ja) * 2000-06-09 2003-12-02 ザ プロクター アンド ギャンブル カンパニー ラテックスへの暴露を減少するための方法及びアイテム

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9359283B2 (en) 2012-05-31 2016-06-07 Micromidas, Inc. Polyhydroxyalkanoate derivatives, preparation and uses thereof
US9688603B2 (en) 2012-05-31 2017-06-27 Micromidas, Inc. Polyhydroxyalkanoate derivatives, preparation and uses thereof

Also Published As

Publication number Publication date
AU2002225827A1 (en) 2002-05-06
US7094840B2 (en) 2006-08-22
WO2002034857A3 (fr) 2003-01-09
US20060247390A1 (en) 2006-11-02
ES2362405T3 (es) 2011-07-04
JP2004512419A (ja) 2004-04-22
WO2002034857A2 (fr) 2002-05-02
ATE510898T1 (de) 2011-06-15
EP1330503A2 (fr) 2003-07-30
US20020068810A1 (en) 2002-06-06

Similar Documents

Publication Publication Date Title
EP1330503B1 (fr) Compositions contenant des polyhydroxyalcanoates et des monomères réactifs
Van der Walle et al. Properties, modifications and applications of biopolyesters
AU740068B2 (en) Polyhydroxyalkanoate molding compositions
EP0428620B1 (fr) Méthode pour la plastification de polymères de lactide.
JPH07502069A (ja) ポリラクチド含有ホットメルト接着剤
JPH09505615A (ja) 乳酸のポリエステルを含む生物分解性／肥料化可能なホットメルト接着剤
US5711842A (en) Adhesion process
JPH05271638A (ja) ポリヒドロキシブチレート／ヒドロキシバレレートベースホットメルト接着剤
NZ230246A (en) Biodegradable polyester compositions containing lactide polymers
CA2156658A1 (fr) Procede de couchage par fusion pour papier et carton
KR20050006179A (ko) 반응성 압출에 의해 수득되는 생분해성 폴리에스테르
EP3356488B1 (fr) Adhésif thermofusible non réactif, sa fabrication et son utilisation
US20070293635A1 (en) Alkanoic Acid Ester Monomer Compositions and Methods Of Making Same
JPS5847432B2 (ja) 熱可塑性コポリエステル
JP2023011717A (ja) 生分解性ホットメルト接着剤
US6780911B2 (en) Low molecular weight polyhydroxyalkanoate molding compositions
JP2004507601A (ja) 非ブロッキングポリマー製品
JP2002088334A (ja) 生分解性ホットメルト接着剤
WO1998014326A1 (fr) Composition polymere
CA2166613C (fr) Procede de collage
JP2003137983A (ja) ポリ乳酸

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030425

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

17Q First examination report despatched

Effective date: 20080129

RTI1 Title (correction)

Free format text: COMPOSITIONS COMPRISING POLYHYDROXYALKANOATES AND REACTIVE MONOMERS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: METABOLIX, INC.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2362405

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20110704

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60144704

Country of ref document: DE

Effective date: 20110707

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110826

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60144704

Country of ref document: DE

Effective date: 20120228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110525

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20200910

Year of fee payment: 20

Ref country code: GB

Payment date: 20200910

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20200908

Year of fee payment: 20

Ref country code: ES

Payment date: 20201111

Year of fee payment: 20

Ref country code: IT

Payment date: 20201008

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60144704

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20211024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20211024

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20211026